CN104232072A - Phosphate anhydrous fracturing fluid gelling agent and preparation and applications thereof - Google Patents

Phosphate anhydrous fracturing fluid gelling agent and preparation and applications thereof Download PDF

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Publication number
CN104232072A
CN104232072A CN201310248381.0A CN201310248381A CN104232072A CN 104232072 A CN104232072 A CN 104232072A CN 201310248381 A CN201310248381 A CN 201310248381A CN 104232072 A CN104232072 A CN 104232072A
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China
Prior art keywords
alcohol
phosphoric acid
gelling agent
anhydrous
preparation
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CN201310248381.0A
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CN104232072B (en
Inventor
薛小佳
徐永高
慕立俊
赵振峰
李宪文
张矿生
吕海燕
吴江
范华波
刘静
李志忠
李楼楼
刘锦
吕宝强
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China Petroleum and Natural Gas Co Ltd
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China Petroleum and Natural Gas Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/64—Oil-based compositions

Abstract

The invention relates to a phosphate anhydrous fracturing fluid gelling agent and a preparation method thereof. The preparation method comprises the following steps: by taking phosphoric acid, phosphorus pentoxide and C12-C18 alcohol as raw materials, reacting for 4-6 hours at a temperature of 60-70 DEG C so as to obtain a monoalkyl phosphate ester, wherein the molar ratio of phosphoric acid to phosphorus pentoxide to the C12-C18 alcohol is (1.3 to 1.3 to 1)-(1.1 to 1.1 to 1); and reacting the monoalkyl phosphate ester with a mixed alcohol of propyl alcohol or/and butyl alcohol, amyl alcohol, hexyl alcohol or/and capryl alcohol so as to obtain a dialkyl phosphate ester, wherein the molar ratio of the mixed alcohol to the monoalkyl phosphate ester is (4 to 1)-(2 to 1), and the mixed alcohol comprises 7-10% of propyl alcohol and/or butyl alcohol, 20-40% of amyl alcohol, and 50-60% of hexyl alcohol or/and capryl alcohol in percentage by mass. The phosphate gelling agent is good in flowability, suitable for continuous fracturing construction, and low in cost, and can, with short-carbon-chain alkanes, form an anhydrous fracturing fluid with a viscosity of 90-140 mPa.s.

Description

A kind of anhydrous gelling agent of phosphoric acid ester and Synthesis and applications thereof
Technical field
The present invention relates to the anhydrous gelling agent of a kind of phosphoric acid ester and Synthesis and applications thereof.
Background technology
Chinese patent CN00100278.3 discloses a kind of oil-base aluminium phosphate gelatinizer for fracture liquid and preparation method thereof.This oil-base aluminium phosphate gelatinizer for fracture liquid is by short carbon chain alkyl (C 1-C 4), moderate-length alkyl chain length (C 6-C 10) and Long carbon chain alkyl (C 12-C 18) aluminum dialkyl phosphate that forms and solvent toluene composition thereof, its preparation process is: (1) triethyl phosphate and the obtained poly phosphate intermediate of Vanadium Pentoxide in FLAKES reaction; (2) poly phosphate intermediate and butanols, penta octanol, the alcohol mixture reaction of 10 six to stearyl alcohol generates dialkyl phosphate intermediate; (3) dialkyl phosphate and reacting aluminum sulfate generate aluminum dialkyl phosphate; (4) add toluene solvant, be made into jelling agent.The weak point of this technology is: (1) adds toluene solvant in synthetic gelling agents process, easily to environment, is unfavorable for environmental protection; (2) aluminum dialkyl phosphate of the method synthesis is adopted to employ Long carbon chain alcohol, the finished product prepared mostly is high-viscous liquid or cream solid, poor fluidity, site operation energy consumption large (often needing to heat dosing) causes trouble to on-the-spot pressing crack construction.
Summary of the invention
The object of this invention is to provide a kind of anhydrous gelling agent of phosphoric acid ester of applicable pressing crack construction, energy and short chain alkanes, as pentane, hexane etc. form good frozen glue, have good flowing properties, formation injury is few, the easily feature of the row of returning.
The object of the invention is to be realized by following technical scheme:
The anhydrous gelling agent of phosphoric acid ester, the dialkyl phosphate be made up of the alcohol mixture of monoalkyl phosphoric acid esters and propyl alcohol, butanols, amylalcohol, hexanol and octanol.
The preparation method of the anhydrous gelling agent of phosphoric acid ester of the present invention:
(1) with phosphoric acid, Vanadium Pentoxide in FLAKES and higher alcohols (C 12-C 18) be raw material, through reacting obtained monoalkyl phosphoric acid esters;
Phosphoric acid, Vanadium Pentoxide in FLAKES and higher alcohols (C 12-C 18) at 60-70 DEG C, react 4-6 hour generation monoalkyl phosphoric acid esters, phosphoric acid, Vanadium Pentoxide in FLAKES and higher alcohols (C 12-C 18) reaction time mol ratio be 1.3:1:1-1.1:1:1;
(2) alcohol mixture of monoalkyl phosphoric acid esters and propyl alcohol and/or butanols, amylalcohol, hexanol and/or octanol reacts and generates dialkyl phosphate;
Phosphoric acid, Vanadium Pentoxide in FLAKES and higher alcohols (C 12-C 18) to react at 80-90 DEG C with alcohol mixture and generate dialkyl phosphate in 7-10 hour;
When monoalkyl phosphoric acid esters and alcohol mixture react, the mol ratio of alcohol mixture and monoalkyl phosphoric acid esters is 4:1-2:1, and the quality composition of alcohol mixture is that propyl alcohol and/or butanols account for 7%-10%, and amylalcohol accounts for 30-40%, and hexanol and/or octanol account for 50-60%.
Advantage of the present invention is:
(1) containing short carbon chain alkyl (C 1-C 4), medium alkyl chain length (C 6-C 10), good flowing properties, pressing crack construction is simple to operate, and pentane, hexane etc. can be made to form frozen glue, and the gelled fracturing fluid of formation has good temperature and shearing sustainability.
(2) plastic speed is fast, is applicable to the continuous pressing crack construction of the complex reservoirs such as hypotonic, low pressure, high water sensitivity.
(3) the present invention is in building-up process, does not introduce the organic solvents such as toluene, can not to environment.
(4) cost of material of the present invention is cheap, and cost is lower.
Embodiment
Embodiment 1:
(1) first in the there-necked flask of 250mL that mechanical stirrer, prolong and thermometer are housed, 25g phosphoric acid is added, 20g Vanadium Pentoxide in FLAKES and 26g lauryl alcohol, at 60 DEG C, isothermal reaction 5h.Isothermal reaction is complete, is cooled to 50 DEG C, holding temperature, stops stirring.Obtain poly phosphate intermediate.
(2) by the propyl carbinol by 8g, the Pentyl alcohol of 18g, the alcohol mixture of the n-Octanol composition of 30g is added in another there-necked flask, and 50 DEG C, isothermal reaction 1h, obtains the alcohol mixture of 56g, stops stirring for subsequent use.
(3) alcohol mixture of the 56g of 50 DEG C is all joined in monoalkyl phosphoric acid esters flask.At 90 DEG C, isothermal reaction 6h.Obtain dialkyl phosphate.
In 100ml Skellysolve A, add the sodium metaaluminate of 1.0g by the anhydrous fracturing fluid thickener of the phosphoric acid ester of above-mentioned gained, 3.0-6.0g, the anhydrous fracturing liquid of viscosity at 90-140mPas in 30-60s, can be formed.
Embodiment 2:
(1) first in the there-necked flask of 250mL that mechanical stirrer, prolong and thermometer are housed, 22g phosphoric acid is added, 20g Vanadium Pentoxide in FLAKES and 26g lauryl alcohol, at 70 DEG C, isothermal reaction 5h.Isothermal reaction is complete, is cooled to 50 DEG C, holding temperature, stops stirring.Obtain poly phosphate intermediate.
(2) by the n-propyl alcohol by 10g, the Pentyl alcohol of 20g, the alcohol mixture of the n-hexyl alcohol composition of 35g is added in another there-necked flask, and 50 DEG C, isothermal reaction 1h, obtains the alcohol mixture of 65g, stops stirring for subsequent use.
(3) alcohol mixture of the 65g of 50 DEG C is all joined in monoalkyl phosphoric acid esters flask.At 90 DEG C, isothermal reaction 6h.Obtain dialkyl phosphate.
In 100ml normal hexane, add the sodium metaaluminate of 1.0g by the anhydrous gelling agent of the phosphoric acid ester of above-mentioned gained, 3.0-6.0g, the anhydrous fracturing liquid of viscosity at 90-140mPas in 30-60s, can be formed.

Claims (3)

1. a preparation method for the anhydrous gelling agent of phosphoric acid ester, is characterized in that:
(1) with phosphoric acid, Vanadium Pentoxide in FLAKES and C 12-C 18alcohol is raw material, reacts and generate monoalkyl phosphoric acid esters in 4-6 hour at 60-70 DEG C; Phosphoric acid, Vanadium Pentoxide in FLAKES and C 12-C 18the mol ratio of alcohol is 1.3:1.3:1-1.1:1.1:1;
(2) monoalkyl phosphoric acid esters and propyl alcohol are or/and butanols, amylalcohol, hexanol generate dialkyl phosphate or/and the alcohol mixture of octanol reacts; The mol ratio of alcohol mixture and monoalkyl phosphoric acid esters is 4:1-2:1; Alcohol mixture quality composition be propyl alcohol or/and butanols accounts for 7%-10%, amylalcohol accounts for 20-40%, and hexanol is or/and octanol accounts for 50-60%.
2. the anhydrous gelling agent of phosphoric acid ester, is characterized in that: it is dialkyl phosphate prepared by method according to claim 1.
3. the application of the anhydrous gelling agent of phosphoric acid ester, it is characterized in that: in 100ml Skellysolve A, add the sodium metaaluminate of the anhydrous gelling agent of 1.0g phosphoric acid ester according to claim 2 and 3.0-6.0g, in 30-60s, form the anhydrous fracturing liquid of viscosity at 90-140mPas.
CN201310248381.0A 2013-06-21 2013-06-21 A kind of phosphoric acid ester waterless gelling agent and its preparation and application Active CN104232072B (en)

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Cited By (4)

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CN106566490A (en) * 2016-10-25 2017-04-19 中国石油大学(华东) Oil-based drilling fluid shear strength-improving agent with aluminum phosphate structure and preparation method thereof
CN106883834A (en) * 2015-12-15 2017-06-23 中国石油天然气股份有限公司 A kind of fracturing fluid for shale gas pressure break and preparation method thereof
CN108285782A (en) * 2017-01-10 2018-07-17 中国石油化工股份有限公司 A kind of lower carbon number hydrocarbons gelling agent of polyalcohol synergy and preparation method thereof
CN108300449A (en) * 2018-03-16 2018-07-20 中国石油大学(华东) A kind of ethers fracturing fluid

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106883834A (en) * 2015-12-15 2017-06-23 中国石油天然气股份有限公司 A kind of fracturing fluid for shale gas pressure break and preparation method thereof
CN106566490A (en) * 2016-10-25 2017-04-19 中国石油大学(华东) Oil-based drilling fluid shear strength-improving agent with aluminum phosphate structure and preparation method thereof
CN106566490B (en) * 2016-10-25 2018-02-09 中国石油大学(华东) A kind of oil base drilling fluid extracting and cutting agent with aluminium phosphate structure and preparation method thereof
CN108285782A (en) * 2017-01-10 2018-07-17 中国石油化工股份有限公司 A kind of lower carbon number hydrocarbons gelling agent of polyalcohol synergy and preparation method thereof
CN108300449A (en) * 2018-03-16 2018-07-20 中国石油大学(华东) A kind of ethers fracturing fluid

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